Process for refining mineral oil



Patented July 26,

; UNITED STATES PATENT OFFICE 2,124,808 I I .rnooass roa narmmc man. on)

No Drawing. Application November 6, 1933, Se-

rial No. 896,910. 1928 This invention relates to extraction methods of refining mineral oils, and is particularly concerned with methods for extracting such oils by means of a selective solvent in the presence of benzol or an equivalent auxiliary solvent.

It has been known in the art that crude petroleum .oils, lubricating, transformer and spindle oils, kerosenes, heavy or light naphthas, etc., can be separated into groups-of components by extraction with suitable selective solvents. A large number of such solvents are available for the purpose. The present invention is particularly (but not exclusively) directed to an improvement in, methods of extracting mineral oils with furfural or acetone, which improvement is analogous to the one claimed for SO: in Patent No. 1,945,516, which issued upon our copending application, Serial No. 379,310, filed July 18, 1929, of which this is a continuation in part.

The invention is based on the discovery that the extraction characteristics of substantially any solvent which is capable of separating a mineral oil into twocomponent groupsone more soluble therein than the other-can be markedly modified by introducing, for example into the extraction mixture, a quantity of benzol or other suitable substance, such as toluol and/or other aromatics, or ether, or chloroform, which solvent. I

The type of selective solvents whose effective ness as the extracting agents in refining mineral oils can be improved by practicing this invention is illustrated by liquid S02, furfural, and acetone. These specific examples represent, however, only typical solvents of a large number of known selective solvents capable of separating mineral oils into aromatic and non-aromatic components (sometimes referred to as naphthenic and parafilnic or as non-paraflinic and paraflinic), which. solvents are intended to be within the scope of this invention.

Likewise, the auxiliary solvents, whose 'pres-,

ence in the extraction mixtures improves the efficacy of extraction, are merely represented by benzol, and aromatic hydrocarbons, in or by ether, or by chloroform, or their mixtures, but may be selected fromv a number of other fluid substances which produce the desired effect, and a which can be relatively easily separated from the material being treated, for example by distillation, and have no detrimentaleii'ect on the re- 'ilned products.

It should be noted that, while it may be preferable sometimes to select the auxiliary solvents general,

In the Netherlands July 23,

" 5 Claims. (on. 196-13) from relatively volatile liquids chemically or physically related to benzol (such as aromatic hydrocarbons) and which usually are miscible in all proportions with the main solvent and the. oil being treated, the invention is not intended to be limited to such solvents. Other substances, such as ether and chloroform. were found to possess the property of improving extraction -characteristics of various liquids which may be used as the main solvents, and these relatively volatile liquids are to be considered as equiva lents of benzol for the purpose of this, specification and the appended claims.

It will be understood, therefore, that the present invention is to include within its scope the extraction processes employing a selective solvent (which may be a single substance or a mixture of suitable substances) and wherein extraction is carried out in the presence of an auxiliary solvent having an action similar to that of benzol, i. e. causing an increase in the efiiciency of separating a mineral oil into its components, which may be the naphthenic and paraflinic portions of the oil.

Generally speaking,'the efliciency of extraction is determined by the solvent power and the selectivity of the solvent (or solvent mixture) with regardto the components of the mixture will hereafter be referred tov as the auxiliary ured by and compared with the relative yields of the rafllnate ofthe desired purity in cases where the mass or volume of the main or sel ec tive solvent is kept constant.

If the extraction efliciency is to be compared in cases where the relative yield is fixed, whilst also the mass or volume of the main or selective solvent. is kept constant, then the quality of the rafflnate may be taken as the measure of the eiilciency.

The efllciency of the various extractions mayv also be measured by comparing the extent to which the solvent is conserved, if the same rafnnate is made with orwithout the use of the auxiliary solvents described in this specification.

By applying this inventio i. e. by using a mainsolvent in the presence of an auxiliary solvent, it becomes possible therefore in extracting hydrocarbon oils to improve the quality and/or quantity of the raflinate and/or to conserve the main solvent.

The method of this invention also provides-a means for improving mineral ,oils having relatively low contents of naphthenic (aromatic) components, which contents it is vdiflicult or immixed solvent on the distribution ratios of the withv index, the no or refractive index, or the stability.

against oxidation. All these properties are dependent on the ratiobetween aromatics (nonparamns) and the paraflins.

The increased extraction eihciency of the mixed solvent process, as compared with the eflicien'cy of the corresponding'single solvent process, is apparently due to the favourable effect of the non-parafiinic and paraflinic components of the oil in the extract and rafllnate phases; in other words, the content of the components preferentially soluble in the selective solvent as compared with that in the rafiinate phase-is increased in the presence of the auxiliary solvent, vso that y when a mixed solvent is used it becomes possible sometimes, under suitable temperature conditions, to produce from'an oil a greater quantity I of the raiiinate, which is richer in paraiiinic components than it would have been possible to ob;- tain if only themain solvent were used.

From the natureof the auxiliary solvents it may beseen that theiraddition to the mainsolvent would normally"pro d uce .a solvent mixture with a greater solvent power for the oilz'than; that'of the main solventso thatuthe selectivity of the solvent-and the yield of theramnatemay *be impaired. Although this'is not necessarily a disadvantageas amain solvent, with an auxiliary solvent added thereto in any case will be use-,v ful in increasing the extraction efiiciency so far as the quality of the rafllnate is concerned, it isv possible to improve this impaired selectivity by suitably lowering. the, temperature of extraction with the resultantadditional increase inthe efilciency of extraction so far as eg the yield of the raffinate is concerned. Ingeneral, the extraction temperature is so selected as to create optimum conditions from .the view points ofeconomy, yield, purity of the products, etc. v

The operating details of putting the invention into practice, such as temperatures, pressures,

5 etc. may vary in different cases, depending upon specific properties of the substances used in each case, or may be controlled by some otherconsideration. For example with a so-called batchextraction the auxiliary solvent may berhixed with "the oil undergoing'treatment either before,

or'at thetime the oilis contacted with the main solvent; the wholeor a part of 'the'auxiliary'solmain solvent prior vent maybe mixed with the to contacting it with the oil. v

-It is preferable, althoughnot. necessary, to

I operatethe process of this invention in a continuous countercurrent manner, i. e. passing the main solvent'countercurrently to and in contact with the oil being extracted through a mixing- :-"an addition of the auxiliary'solvent would be most effective. The extract and raflinate phases h settlin'gzone and adding atleast a portion of the I auxiliary solvent to the-oil-ma'in solvent mixture at apoint, or points, along the mixing-settling zone, and preferably at such a place where such are separated, usually by gravity, and the-main and auxiliarysolvents or the main solvent only" are then'removed from each of the phases'by distillation (both solvents beingremoved together or in separate fstagesy'or by some other suitable means The separated solvents'may becontinually reused. The auxiliary solvent may: be left inthe raffinate if this solvent improvesthe qual-- low content of parafllnic hydrocarbons) were thoroughly contacted with various quantities of furfural, and of furfural-benzoi, of furfurale chloroform, and of furfural-etherj mixtures; in

each case the raflinate (upper) layers were separated, and the'viscosity and retracting indices of solvent-free'portions (raiilnates) were determined. The following table contains the pertinent data:

auxiliary solvent,,such as benzol, or chloroform, or ether, causesa-marked improvement in the refined product; the results also demonstrate that .non-paraflinic components are extracted in preference to paraflinic components when fur-, fural-benzol mixture is used instead of furfural alone The following example further illustrates some of the effects of extraction temperature upon the efllciency of extraction when a motor oil hav-- ing a viscosity index -.5 is extracted.

i Raflinate on Fur- Ben- Chloro- Temperaparts fural zol form ture of exparts parts parts traction '0. Percent "iscosity yield. index "These data demonstrate that the yield and the degree of refinement of the 'rafiinate' may be conposition of the mixed" solvent, and the selective solvent can be 'conserved, when used with an auxiliary solvent for producing the railinate havz' ing a fixed viscosity index. a

Similar results may be obtained when extracting mineral oils with other selective solvents, such as acetone, in the presence of an auxiliary olvent of the type of benzol, chloroform or ether, 1. e. either a somewhat polar or more often a nonpolar solvent, but whose action is manifested in Y 1 Raflinate Oil Furiural Benzol Ether parts parts parts parts parts 2 viscosity 0 index ntreated oil 1.5366 59 100- 150 None 1.5160 +3 100 150 50 1.5136 +7 100. 150 1. 5115 +11 100, 150 1.5100 +21 Theseresults showtthat the presence of an trolled at will by regulating the extraction tem- "perature andthe relative quantity and the com the extraction processes through an increase in the extraction efficiency.

A series of extractions similar to those demonstrating the use of furfural-auxiliary solvent mixtures werecarried out using acetone as the main The original oil extracted with acetone was-an Edeleanu raflinate having d2o=.8765 and n-,=

The particular feature of the extractions with acetone and acetone-auxiliary solvent mixtures was that while the first extraction could be carried out at about 20 C., the last three extractions required temperatures of about -20 C. in order to produce either about the same or better yield of the rafflnate than obtained with acetone alone. As indicated by gravities and refractive indexes of the raflinates the process of this invention constitutes a decided improvement of the known process using only acetone as a solvent.

It has been also found that various mixtures of selective solvents, such, for example, as liquid SOz-furfural, can be successfully used for extracting mineral oils in the presence of either the individual auxiliary solvents or their mixtures.

While it is practical and may be desirable in some cases to carry out the extraction of mineral oils ,by means of the main and auxiliary solvents at such temperatures, at which the auxiliary solvent is only partially soluble in either the main solvent or theoil being extracted, or in both, it,

should be noted that the extraction process of this invention may be operated at the temperatures at which the auxiliary solvent becomes miscible in all proportions with either the main, 1. e. selective, solvent or the oil, or both.

The main solvents used in this extraction process to separate a mineral oil into two component groups as defined, have the common characteristic that, like liquid S02, acetone or 'furfural, at the extraction temperature they are completely miscible only with the non-parafllnic component group. With the paraflinic component group they are miscible only to a limited extent. Examples ofsuch like selective solvents are: nitromethane, propionltrile, dimethyl sulphate. dimethyl sulphite, methyl formate and several alcohols or esters at suitable temperatures.

, With reference to what has been stated above in respect to the auxiliary solvents, it deserves notice that the particular effect of auxiliary solvents on the extraction efficiency is independent finate phases, and separating the said phases.-

.liquid hydrocarbon oil into contact with furfural 3 ously diluted. On the other hand, oil which may be regarded as being viscous at ordinarytemperatures (say, over seconds at F.-Saybolt universal) would become easy iiowingat the slightly elevated temperatures of extraction with furfural, for example, or some other selective solvent, so thattheir dilution for the purpose of reducing the viscosity would be unnecessary. The use of auxiliary solvents in these cases would serve only the purpose of improving the extraction efliciency through the eflec't of such solvents on the distribution of the components being extractedbetween the extract and raflinate phases, no dilution being necessary. Relatively light aromatic extracts, such as those boiling within gasoline or kerosene ranges, which can be later removed from the products of extraction, may be used with advantage as equivalents of benzol in extracting the oils which are 2. In an extraction process for separating a mineral hydrocarbon oil into two component groups, the steps of contacting a liquid mineral hydrocarbon oil with furfural in the presence ofv toluol under conditions causing the formation of degrees of paramnicity, thesteps of bringing a in the presence of an auxiliary solvent selected under conditions causing the formation of liquid rafllnate and extract phases, and separating the said phases.

4. In an extraction process for separating a hydrocarbon oil into portions having different degrees of parafllnicity, the steps of bringing a liquid hydrocarbon oil into contact with acetone in the presence of an auxiliary solvent selected from the group consisting of: benzol and toluol,

.from the group consisting of: benzol and toluol, F I

under conditions causing the formation of liquid ramnate andextract phases, and separating the said phases.

5. In an extraction process for separating a hydrocarbon oil into portions having diflerent degrees of parafllnicity, the steps of contacting a stream of liquid hydrocarbon oil countercurrently with a stream of a. selective solvent fornonparaflinic hydrocarbons under conditions-causing the formation of liquid ramnate and phases in the presence of an auxiliary solvent selected from the group consisting of: bensoland toluol, a portion'oniy of said auxiliary solvent being initially introduccdinto the oounterflowing streams with the fresh selective solvent, and another portion being into said streams at a point spaced from the'pointof introduction of the selective solventin thedirection of the point of introduction "offthe'initial "'9 oil, and separating said phases. 

